Investigation of the reactivity of the biradical [P(µ-NTer)]2 towards bromoalkanes and follow-up chemistry

Poster presentation by Jan Rosenboom

Jan Rosenboom, Jonas Bresien, Lukas Chojetzki, Axel Schulz, Tim Suhrbier, Alexander Villinger, Ronald Wustrack



Group 15 open-shell singlet biradicals of the type [E(μ-NR)]2 (E = P, As) have been in focus of our group’s research for several years.[1] They can be accessed by reduction of their halogenated precursors (e.g. [ClP(μ-NTer)]2).

It is known from previous research that group 15 biradicals show very high reactivity towards small molecules, e.g. allowing the activation of double and triple bonds.[2] In our current study the reactivity of the biradical [P(μ-NTer)]2 (A, Scheme 1) towards various bromoalkanes was investigated.

Scheme 1. Addition of various bromoalkanes to [P(μ-NTer)]2.


The biradical selectively activated the C−Br bond, forming the addition product B whereone phosphorous atom bears a bromine atom as substituent and the other a varying the organic group R.

The follow-up-chemistry of the [P(μ-NTer)]2-bromoalkane adducts is being studied.

Figure 1. Structure of the bromoalkane adduct to [TerNP]2 as determined by single crystal X-ray diffraction.

Jan joined our group for his Master's thesis in 2019. He is working on the activation and functionalization of C-X bonds using our phosphorus biradicals.


[1] Schulz, A. Group 15 Biradicals: Synthesis and Reactivity of Cyclobutane-1,3-Diyl and Cyclopentane-1,3-Diyl Analogues. Dalton Trans.2018, 47 (37), 12827–12837.

[2] Hinz, A.; Kuzora, R.; Rosenthal, U.; Schulz, A.; Villinger, A. Activation of Small Molecules by Phosphorus Biradicaloids. Chem. Eur. J.2014, 20 (45), 14659–14673.